reagent guide synthetic organic chemistry & materials chemistry

Reagent Guide Synthetic Organic Chemistry & Materials Chemistrywww.TCIchemicals.com
Synthetic Organic Chemistry & Materials Chemistry
We have reviewed our product line-ups and organized them according to the research areas of synthetic organic chemistry and materials chemistry. We hope that this reagent guide will be of assistance to your research and development laboratories. However, this guide is not an all inclusive list of all the reagents we deal in. Please be sure to look up our catalog and visit our website as well to remain updated on the latest information in the various fi elds of your interest.
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The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.
Synthetic Organic Chemistry “Topics” Copper-free Click Reactions .......................................1 Easily Accessible Crystalline CO Surrogate Reagents ......2 Functional Group Transformation & Introducing Reaction Oxidation ........................................................................3 Reduction .......................................................................9 Halogenation .............................................................. 17 Trifl uoromethylation ................................................... 23 Trifl uoromethylthiolation ............................................ 25 Formylation ................................................................. 26 Cyanation .................................................................... 29 Amination .................................................................... 31 Mitsunobu Reaction ................................................... 34 Condensation & Active Esterifi cation ..................... 38 Carbon-Carbon Bond Forming Reactions Carbonyl Olefi nation .................................................. 44 Cross-coupling Reaction Using Transition Metal Catalysts .................................................................. 52
Activation of Non-active Bonds ............................... 69 Synthetic Reagents Metal Reagents for Organic Synthesis ................... 76 Stable Lewis Acids in Aqueous Media ................... 89 Ligands ........................................................................ 91 Asymmetric Organocatalysts .................................102 Chiral Auxiliaries ......................................................108 Chiral Phase-transfer Catalysts .............................110 Optical Resolving Agents .......................................113 Protection & Derivatization ....................................120 Ionic Liquids .............................................................130 Fluorous Solvents ....................................................135 Polymer-supported Reagents .................................137 Building Blocks Boronic Acids & Boronic Acid Derivatives ..........139 Chiral Building Blocks .............................................156 Terminal Acetylenes ................................................180 Azide Compounds ....................................................186
Materials Chemistry Nanocarbon Materials Fullerenes .................................................................190 Carbon Nanotubes ...................................................192 Graphene & Graphene Oxide .................................194 Nanodiamonds .........................................................196 Nanocarbon Unit Structures ..................................198 Electronic Materials Reagents for Solar Cell Research .........................201 Reagents for Secondary Battery ...........................206 OLED Materials ........................................................213 Organic Transistor Materials ..................................219 Molecular Conductors .............................................223 Building Blocks for Semiconducting Polymer .....230 Building Blocks for Small Molecule Semiconductor ...238 Ligands for Functional Metal Complex ................254 Optically Functional Materials Photochromic Compounds .....................................259 Liquid Crystal Materials ..........................................262 Building Blocks for Liquid Crystals .......................270 Organic Nonlinear Optical Materials ....................274 Materials for Near Infrared Absorption .................276
Magnetic Materials Magnetic Metal Complexes ...................................277 Organic Radicals .....................................................281 Magnetic Ionic Liquids ............................................283 Functional Organic Dyes Coumarin Dyes .........................................................284 Porphyrin & Phthalocyanine Dyes ........................286 Perylene Dyes ..........................................................289 Cyanine & Squarylium Dyes ..................................291 Dipyrromethene Dyes ..............................................293 Xanthene Dyes .........................................................294 DCM Dyes ................................................................296 Quinacridone Dyes ..................................................297 Organic-Inorganic Hybrid Materials Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands .....................................................298
Polymer Research Reagents Polymers ...................................................................316 Monomers .................................................................319 Polymerization Inhibitors .........................................320 Polymerization Initiators ..........................................321 Polymerization Catalysts ........................................325 Precise Polymerization Reagents .........................328 Resin Additives ........................................................333 Photopolymer Research Reagents ........................341 Macrocycles for Host-Guest Chemistry Macrocycles for Host-Guest Chemistry ...............342 Other Reagents Building Blocks for Dendrimers .............................348 Derivatizing Reagents for Solubility Improvement ...351
INDEX ...........................................................................365
TCI International Offi ces .............................................376 TCI Distributors ............................................................377
If you are looking for products in the field of Bioscience & Analytical Science, please see below.
Reagent Guide 8th Edition Bioscience & Analytical Science Bioscience Example : Antibodies / Sugars / Nucleosides / Amino Acids / Lipids / Terpenes / Steroids etc. Analytical Science Example : GC Derivatizing Reagents / Labeling Reagents for HPLC / Chromatography Columns for HPLC / Derivatization Reagents for Mass Spectrometry etc.
Contents
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1This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.
Copper-free Click Reactions
Among the “click chemistry” proposed by K. B. Sharpless in 2001, the Huisgen cyclization using azides and terminal alkynes has been widely used in various reseach fi elds such as chemical biology and material science due to its excellent chemoselectivity.1) Generally, the Huisgen cyclization requires some copper salts to promote the reactions. However, use of the copper salt-mediated click reactions for in vivo applications is often highly restricted owing to the toxicity of active oxygen in vivo generated by the copper salt. Therefore, the development of advanced click reactions without using any copper salt has been investigated. In the research fields using copper-free click reactions, a number of studies aimed for in vivo
applications such as living cells and biological experiments on animals have been reported. To be suitable for such purposes, molecular design of alkyne derivatives has been performed mainly to improve two chemical properties of second order reactions, rate constant and lipophilicity (log P). In 2004, C. R. Bertozzi et al. have reported the copper-free click reaction using highly-strained
cyclooctyl groups as reactants. These cyclooctyl compounds satisfy the above mentioned two requests and are widely used as a molecular tool to reveal the metabolic systems.2) Recently, they have been used to construct the microenvironment of hydrogels supporting the basis of regenerative medicine research. Because of that, Bertozzi et al. have suggested general and accessible experimental procedures for researchers who don’t do major synthetic organic chemistry, and their practical examples can be referred to in the research article.3) Furthermore, van Delft et al. have developed more eff ective cyclooctyl compounds usable for in vivo
bioorthogonal and 3D imaging.3) For instance, ADIBO-amine and BCN-amine are suitable molecules for the copper-free click reaction in biological research because they have low lipophilicity and high reactivity. Especially, ADIBO-amine is used for PEGylation of proteins and nuclear imaging by positron emission tomography (PET) using a fl uorine-18 [18F] radioisotope. As stated above, ADIBO-amine and BCN-amine are expected to be powerful versatile tools for the copper-free click reaction because they can also be used for surface reforming of solid materials and chemical modifi cation of organic molecules in material science research as well as live imaging and microarray analysis in life science research.
H H
2
Cyclooctyl group [2+3] cycloaddition with azides High reaction rate constant
Amino group Easy to modify
BCN-amine
ADIBO-amine
(ADIBO-amine) 25mg B4062 N-(1R,8S,9s)-Bicyclo[6.1.0]non-4-yn-9-ylmethyloxycarbonyl-
1,8-diamino-3,6-dioxaoctane (BCN-amine) 25mg 100mg
References 1) H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004. 2) N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc. 2004, 126, 15046. 3) E. M. Sletten, C. R. Bertozzi, Acc. Chem. Res. 2011, 44, 666. 4) a) J. Dommerholt, S. Schmidt, R. Temming, L. J. A. Hendriks, F. P. J. T. Rutjes, J. C. M. van Hest, D. J. Lefeber, P. Friedl, F.
L. van Delft, Angew. Chem. Int. Ed. 2010, 49, 9422. b) M. F. Debets, S. S. van Berkel, S. Schoff elen, F. P. J. T. Rutjes, J. C. M. van Hest, F. L. van Delft, Chem. Commun.
2010, 46, 97.
rganic C hem istry
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2 The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.
Easily Accessible Crystalline CO Surrogate Reagents
Carbon monoxide (CO) is used as a signifi cant carbonyl group-introducing reagent in organic synthesis. A number of synthetic reactions using CO have been developed. Because CO is a colorless, odorless and toxic gas at room temperature, it is necessary to pay minute attention when using it. For that reason, in the fi eld of the synthetic chemistry using CO, the development of CO surrogate reagents as well as the study of novel synthetic reactions has proceeded.
H O
CO
Manabe et al. have investigated novel CO surrogate agents focused on formic acid derivatives and found that 2,4,6-trichlorophenyl formate can act functionally as a CO equivalent.1) This compound is a stable crystalline solid at room temperature and it rapidly decomposes into CO and 2,4,6-trichlorophenol by treatment with a trialkylamine. In situ generated CO is successfully applied to the palladium-catalyzed carbonylation of aryl/alkenyl halides and trifl ates to give their 2,4,6-trichlorophenol esters. Continuously, the given esters can be transformed into the corresponding carboxylic acid derivatives by the reaction with various nucleophiles. This carbonylation reaction is a highly practical synthetic method since it does not decrease the reaction yields even in gram-scale reactions.2)
R1 X R1 O
Pd(OAc)2 [A1424]
O
Subsequently, Manabe et al. have developed the reductive carbonylation using N-formylsaccharin as a CO equivalent.3) In this reaction, palladium acetate is used as a catalyst and the reaductive carbonylation of aryl bromides is accomplished in combination with triethylsilane as a nucleophile. The hydrogen atom on a formyl group of formed aldehydes is introduced by the addition of the hydride species from triethylsilane.
BrR
N
Br
N
DMF, 75-85 oC
HHydrogenation of hydride species from Ei3SiH
In a case using 2,4,6-trichlorophenyl formate together with other nucleophiles, the carbonylation reaction tends to be complicated because of the nucleophilicity of 2,4,6-trichlorophenol formed as a byproduct. However, in the carbonylation reaction using N-formylsaccharin, hydrosilanes can be directly used as a nucleophile because the nucleophilicity of formed saccharin is suffi ciently inert.
Product No. Product Name Unit Size T3121 2,4,6-Trichlorophenyl Formate 1g 5g F0854 N-Formylsaccharin 5g 25g
References 1) T. Ueda, H. Konishi, K. Manabe, Org. Lett. 2012, 14, 5370. 2) H. Konishi, T. Ueda, K. Manabe, Org. Synth. 2014, 91, 39. 3) T. Ueda, H. Konishi, K. Manabe, Angew. Chem. Int. Ed. 2013, 52, 8611.
Easily Accessible Crystalline CO Surrogate Reagents S yn th et ic O rg an ic C he m is try
M at er ia ls C he m is try
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Oxidation
Oxidation, making its target substance lose electrons, is one of the most basic reactions in organic chemistry and is exemplifi ed by the combination with oxygen or a dehydrogenation reaction. In particular, it is often used for the transformation of alcohols to the corresponding aldehydes, ketones or carboxylic acids. Heavy metal compounds, such as chromium (VI) oxide and potassium permanganate, have been exploited for many years. Especially, chromium (VI) oxide has been utilized abundantly, based on the report of the control of oxidization powers by Jones or Sarett.1) Furthermore, chromium (VI) oxide have been improved as the Collins reagent2), PCC3) and PDC4) and are used in many fi elds. On the other hand, the Dess-Martin periodinane5), the Mukaiyama oxidizing agent6) and oxoammonium salts have been developed without containing harmful metals. Moreover, oxidation reactions employing inexpensive sodium hypochlorite or molecular oxygen have also been reported in the presence of oxidation catalysts such as tetrapropylammonium perruthenate (TPAP)7) and TEMPO8). This section shows the typical oxidizers and the catalysts used for oxidation reactions.
Metal Oxidants
ruthenium(IV) 100mg
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Product No. Product Name Unit Size L0021 Lead Tetraacetate (contains Acetic Acid) 25g 500g O0414 Osmium Catalyst supported on Magnetite (0.07-0.09mmol/g) 1g O0308 Osmium Tetroxide (4% in Water) 10mL P1910 Phosphomolybdic Acid Hydrate 25g 100g P1742 Potassium Permanganate 300g P0930 Pyridinium Chlorochromate 25g 100g 500g P0931 Pyridinium Dichromate 25g 100g 500g P1088 Pyridinium Fluorochromate 5g Q0058 Quinolinium Dichromate 10g 25g S0815 Silver(II) Pyridine-2-carboxylate 1g 5g T1803 Tetrabutylammonium Perrhenate 1g 5g T1559 Tetrapropylammonium Perruthenate 1g 5g
Perchlorates
B2897
N
Organic Peroxides
CH3
CH3
OOH
Oxidation S yn th et ic O rg an ic C he m is try
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C0357
C
O
OOH
Cl
C2223
C
CH3
CH3
OOH
D3411
O
O
O
Product No. Product Name Unit Size B3152 Benzoyl Peroxide (wetted with ca. 25% Water) 25g B3497 Bis(trimethylsilyl) Peroxide (contains Hexamethyldisiloxane) (ca. 30% in Hexane) 5g B3153 tert-Butyl Hydroperoxide (70% in Water) 100g C0357 3-Chloroperoxybenzoic Acid (contains ca. 30% Water) 25g 250g C2223 Cumene Hydroperoxide (contains ca. 20% Aromatic Hydrocarbon) 100g D3411 Di-tert-butyl Peroxide 100mL M0927 Monoperoxyphthalic Acid Magnesium Salt Hexahydrate 25g 500g
Hypervalent Iodine Compounds
Oxidation S ynthetic O
rganic C hem istry
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N-Oxides
D3219
N
O
ClCl
D3220
N
O
N(CH3)2
xH2O.
L0069
Product No. Product Name Unit Size D3219 2,6-Dichloropyridine N-Oxide 5g D3220 4-(Dimethylamino)pyridine N-Oxide Hydrate 1g 5g L0069 2,6-Lutidine N-Oxide 25g M0981 4-Methylmorpholine N-Oxide (50% in Water, ca. 4.8mol/L) 25mL 500mL M2192 4-Methylmorpholine N-Oxide 5g 25g P0557 Pyridine N-Oxide 25g 500g T1362 Trimethylamine N-Oxide Anhydrous 1g 5g T0466 Trimethylamine N-Oxide Dihydrate 25g 500g
TEMPOs
A1348
N
HN
O
CH3
CH3
CH3
CH3
C
O
CH3
H0878
N
O
O
CH3
CH3
CH3
CH3
C
O
I0908
N
O
CH3
CH3
CH3
CH3
O
Organic Bismuth Compounds
T1837
Bi
Cl
Cl
T2507
Bi
CH3
CH3
BF4
T1956
Bi
Cl
Cl
CH3O
OCH3
OCH3
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T2038
Others
A2065
N
NH
O
CH3
CH3
CH3
CH3
BF4
C
O
CH3
C1806
(NH4)2Ce(NO3)6
B2151
S2O8
Bu
N
Bu
BuBu
2
2
T0617
O
O
Br
BrBr
Br
B0656
Oxidation S ynthetic O
rganic C hem istry
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Product No. Product Name Unit Size B2188 N-tert-Butylbenzenesulfi nimidoyl Chloride 1g 5g H0362 tert-Butyl Hypochlorite 25g 500g C1326 (2R,8aS)-(+)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent] 1g 5g C1327 (2S,8aR)-(-)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent] 1g 5g C0076 Chloramine T Trihydrate 25g 500g T0061 Chloranil 25g 500g T0970 o-Chloranil 5g 25g D0318 Dichloramine T 25g 500g H1404 2-Hydroxy-2-azaadamantane 200mg 1g 5g I0074 N-Iodosuccinimide 5g 25g 100g M2274 1-Methyl-3-[6-(methylsulfi nyl)hexyl]imidazolium p-Toluenesulfonate 1g 5g M2321 1-Methyl-3-[6-(methylthio)hexyl]imidazolium p-Toluenesulfonate 1g 5g O0310 Potassium Peroxymonosulfate [>45%(T) as KHSO5] 25g 500g P0998 Pyridine - Sulfur Trioxide Complex 25g 100g 500g T1559 Tetrapropylammonium Perruthenate 1g 5g
Many oxidizing agents may cause combustion or explosion upon mixture with fl ammable materials or upon exposure to heat, shock, and friction etc. Suffi cient safety measures, such as using safety shields, wearing protective equipment, and using extreme caution should be taken when working with these reagents as well as disposing of the reagents.
References 1) K. Bowden, I. M. Heilbron, E. R. H. Jones, J. Chem. Soc. 1946, 39; Review: S. V. Ley, A. Madin, Comprehensive Organic Synthesis 1991, 7, 253.
2) J. C. Collins, W. W. Hess, F. J. Frank, Tetrahedron Lett. 1968, 9, 3363. 3) E. J. Corey, J. W. Suggs, Tetrahedron Lett. 1975, 16, 2647. 4) E. J. Corey, G. Schmidt, Tetrahedron Lett. 1979, 20, 399. 5) D. B. Dess, J. C. Martin, J. Org. Chem. 1983, 48, 4155; R. E. Irekand, L. Liu, J. Org .Chem. 1993, 58, 2899. 6) J. Matsuo, D. Iida, K. Tatani, T. Mukaiyama, Bull. Chem. Soc. Jpn. 2002, 75, 223. 7) W. P. Griffi th, S. V. Ley, G. P. Whitcombe, A. D. White, J. Chem. Soc., Chem. Commun. 1987, 1625; Review: S. V. Ley, J. Norman, W. P. Griffi th, S. P. Marsden, Synthesis 1994, 639.
8) O. L. Lebelev, S. N. Kazarnovskii, Zhur. Obshch. Khim. 1960, 30, 1631; Review: A. E. J. de Nooy, A. C. Besemer, H. van Bekkum, Synthesis 1996, 1153.
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Reduction Reduction is a chemical reaction in which the target substances receive electrons, and is one of the most fundamental reactions in organic chemistry including the deoxygenation reaction and the hydrogenation reaction. The well-known reducing agents include metal hydrides such as LiAlH41), boranes used in the hydride reduction, and hydrazine used in the Wolff-Kishner reduction.2) Sodium tris(1,1,1,3,3,3-hexafl uoroisopropoxy)borohydride (1) is a selective reducing agent developed by Toshima et al. Aldehydes are selectively reduced in the presence of ketones and other reducible functions using 1 to aff ord the corresponding primary alcohols in high yields.3)
Y. 94%
CH3 CHO
O OTBS
OCH(CF3)2
B
OCH(CF3)2
OCH(CF3)2H
Table. Comparison of reactivities of hydride reducing agents for carbonyl compounds and imines
Reagents
Reactions
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Metal Hydrides Aluminum Hydrides
Product No. Product Name Unit Size D2972 Diisobutylaluminum Hydride (17% in Toluene, ca. 1.0mol/L) 100mL 500mL D2971 Diisobutylaluminum Hydride (19% in Hexane, ca. 1.0mol/L) 100mL 500mL L0203 Lithium Aluminum Hydride (Powder) 25g 100g L0170 Lithium Aluminum Hydride (10% in Tetrahydrofuran, ca. 2.5mol/L) 100mL L0159 Lithium Tri-tert-butoxyaluminum Hydride (ca. 30% in Tetrahydrofuran, ca. 1.0mol/L) 100mL S0467 Sodium Bis(2-methoxyethoxy)aluminum Dihydride (70% in Toluene, ca. 3.6mol/L) 25g 100g 500g
Tin Hydrides
CH3(CH2)3 H
Product No. Product Name Unit Size T1473 Tributyltin Hydride (stabilized with BHT) 25g 250g
Other Metal Hydrides
ZrH Cl
Product No. Product Name Unit Size S0481 Sodium Hydride (60%, dispersion in Paraffi n Liquid) 100g 500g Z0010 Zirconocene Chloride Hydride 1g 5g 25g
Reduction S yn th et ic O rg an ic C he m is try
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Borohydrides
B1139
(2.6-3.0mmol/g) 5g 25g P1681 Potassium Borohydride 25g 100g P1380 Potassium Tri-sec-butylborohydride (ca. 1.0mol/L in Tetrahydrofuran) Price on request S0480 Sodium Borohydride 25g 100g 500g S0396 Sodium Cyanoborohydride 5g 25g 250g S0394 Sodium Triacetoxyborohydride 25g 100g S0810 Sodium Tris(1,1,1,3,3,3-hexafl uoroisopropoxy)borohydride 5g T0917 Tetrabutylammonium Borohydride 5g 25g T0852 Tetramethylammonium Borohydride 5g 25g T1553 Tetramethylammonium Triacetoxyborohydride 5g 25g
Boranes Borane Complexes
Product No. Product Name Unit Size B1827 1,2-Bis(tert-butylthio)ethane Borane 1g T2346 Borane - Tetrahydrofuran Complex (8.5% in Tetrahydrofuran, ca. 0.9mol/L)
(stabilized with Sodium Borohydride) 100mL 500mL D2581 N,N-Diethylaniline Borane 25g 100g D1843 Dimethyl Sulfi de Borane 25mL 100mL
Reduction S ynthetic O
rganic C hem istry
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Borane-Amine Complexes
CH3
T1180
BH3 .
CH2CH3
N
CH2CH3
CH3CH2
T1181
BH3 .
CH3
N
CH3
CH3
Product No. Product Name Unit Size B1264 Borane - tert-Butylamine Complex 25g 100g B4084 Borane - 5-Ethyl-2-methylpyridine Complex 25mL 100mL B3018 Borane - 2-Methylpyridine Complex 5g 25g M0898 Borane - Morpholine Complex 5g 25g B1569 Borane - Pyridine Complex 25mL D1842 Dimethylamine Borane 25g 500g T1180 Triethylamine Borane 25g T1181 Trimethylamine Borane 25g
Other Boranes
Silanes
C1492
CH3
H
CH3
H
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T1896
Si
H
Si
H
T0398
Cl
Si
Cl
Hydrazines, Hydrazides
CH3
Product No. Product Name Unit Size C2648 3-Chlorobenzohydrazide 5g 25g H0697 Hydrazine Anhydrous 10g 100g H0204 Hydrazine Monohydrate (79%) 25g 500g H0172 Hydrazine Monohydrate 25mL 500mL H0169 Hydrazine Dihydrobromide Hydrate 25g 500g H0170 Hydrazine Dihydrochloride 25g 500g
rganic C hem istry
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Product No. Product Name Unit Size H0173 Hydrazine Monohydrobromide 25g 500g H0174 Hydrazine Monohydrochloride 25g 500g I0777 N '-Isopropylidene-2-nitrobenzenesulfonohydrazide 5g
Others
D4311
Product No. Product Name Unit Size D4311 Di-tert-butyl 1,4-Dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate 1g 5g D3775 Diethyl 1,4-Dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate 1g 5g 25g H1221 Hydriodic Acid (57%) 300mL S0494 Samarium(II) Iodide (ca. 0.1mol/L in Tetrahydrofuran) 25mL T0430 Triethyl Phosphite 25mL 500mL T0488 Trimethyl Phosphite 25mL T0519 Triphenylphosphine 25g 500g T1819 Triphenylphosphine Selenide 5g
Many reducing agents may spontaneously ignite on contact with air, or may react violently with water to produce fl ammable gases. Suffi cient safety measures, such as using safety shields, wearing protective equipment, and using extreme caution should be taken when working with these reagents as well as disposing of the reagents.
Hydrogenation Catalysts
Product No. Product Name Unit Size P1785 Palladium 10% on Carbon (wetted with ca. 55% Water) 5g 25g P1491 Palladium 10% on Carbon (wetted with ca. 55% Water) 5g 25g P1701 Palladium 5% on Barium Carbonate 10g P1702 Palladium 5% on Barium Sulfate 5g 25g P1703 Palladium 5% on Calcium Carbonate (poisoned with Lead) 5g 25g P1490 Palladium 5% on Carbon (wetted with ca. 55% Water) 5g 25g P1528 Palladium Hydroxide 20% on Carbon (wetted with ca. 50% Water) 10g 50g P1786 Palladium on SH Silica Gel (0.1mmol/g) 1g P1720 Platinum(IV) Oxide 200mg P1944 Poly(methylphenyl)silane supported Palladium/Alumina Hybrid Catalyst [=Pd / (PSi-Al2O3)] 1g R0075 Rhodium 5% on Carbon (wetted with ca. 55% Water) 1g R0076 Ruthenium 5% on Carbon (wetted with ca. 50% Water) 5g 25g S0487 Skeletal Nickel Catalyst slurry in Water 50g
Asymmetric Hydrogenation Catalysts
R0129
Me
Me
OMe
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R0128
Product No. Product Name Unit Size R0129 RuCl2[(R)-dm-segphos®][(R)-daipen] 200mg 1g R0128 RuCl2[(S)-dm-segphos®][(S)-daipen] 200mg 1g R0131 RuCl2[(R)-dm-segphos®][(R,R)-dpen] 200mg 1g R0130 RuCl2[(S)-dm-segphos®][(S,S)-dpen] 200mg 1g R0133 RuCl2[(R)-xylbinap][(R)-daipen] 200mg 1g R0132 RuCl2[(S)-xylbinap][(S)-daipen] 200mg 1g R0135 RuCl2[(R)-xylbinap][(R,R)-dpen] 200mg 1g R0134 RuCl2[(S)-xylbinap][(S,S)-dpen] 200mg 1g R0139 (R)-RUCY®-XylBINAP 200mg 1g R0138 (S)-RUCY®-XylBINAP 200mg 1g
Ruthenium Complex Catalysts for Asymmetric Hydrogenation of Olefi ns and Functionalized Ketones
R0146
rganic C hem istry
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Product No. Product Name Unit Size R0154 [RuCl(p-cymene)((R)-segphos®)]Cl 200mg 1g R0155 [RuCl(p-cymene)((S)-segphos®)]Cl 200mg 1g R0148 [RuCl(p-cymene)((R)-tolbinap)]Cl 200mg 1g R0149 [RuCl(p-cymene)((S)-tolbinap)]Cl 200mg 1g R0150 [RuCl(p-cymene)((R)-xylbinap)]Cl 200mg 1g R0151 [RuCl(p-cymene)((S)-xylbinap)]Cl 200mg 1g
Ruthenium Complex Catalysts for Asymmetric Transfer Hydrogenation of Ketones
R0123
N
Product No. Product Name Unit Size R0123 RuCl[(R,R)-Fsdpen](p-cymene) 200mg 1g R0122 RuCl[(S,S)-Fsdpen](p-cymene) 200mg 1g R0125 RuCl[(R,R)-Tsdpen](p-cymene) 200mg 1g R0124 RuCl[(S,S)-Tsdpen](p-cymene) 200mg 1g R0127 RuCl[(R,R)-Tsdpen](mesitylene) 200mg 1g R0126 RuCl[(S,S)-Tsdpen](mesitylene) 200mg 1g T3078 (R,R)-Ts-DENEB® 200mg 1g T3077 (S,S)-Ts-DENEB® 200mg 1g
These products were merchandised under the technical tie-up with TAKASAGO INTERNATIONAL CORPORATION. SEGPHOS®, RUCY®, and DENEB® are registered trademarks of TAKASAGO INTERNATIONAL CORPORATION.
References 1) Review: J. Malek, M. Cerny, Synthesis 1972, 217. 2) Review: N. Kishner, J. Russ. Phys. Chem. Soc. 1911, 43, 582; L. Wolff , Ann. 1912, 394, 86; R. O. Hutchins, M. K. Hutchins, Comprehensive Organic Synthesis 1991, 8, 327.
3) Y. Kuroiwa, S. Matsumura, K. Toshima, Synlett 2008, 16, 2523. 4) C. Chatgilialoglu, D. Griller, M. Lesage, J. Org. Chem. 1988, 53, 3641. 5) O. Yamazaki, H. Togo, S. Matsubayashi. M. Yokoyama, Tetrahedron Lett. 1998, 39, 1921.
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Halogenation
Halogenation is a basic and fundamental transformation in organic chemistry, and halogenated compounds are of extreme importance as building blocks in organic synthesis. The development of modern coupling reactions, such as the Suzuki-Miyaura and Mizoroki-Heck reactions, have greatly increased the demand for halogenated compounds as starting materials. In response to this situation, many novel halogenating reagents have been developed.
The page below shows some examples of brominating and iodinating reagents, which have been released recently in our lineup of products.
Example of brominating products: Dibromoisocyanuric acid (DBI) (1), which was fi rst reported by Gottardi, is a mild and highly eff ective
brominating reagent,1,2) and has superior brominating ability when compared with N-bromosuccinimide (NBS), which is frequently used in organic synthesis. For instance, nitrobenzene was converted to the 3-bromonitrobenzene in 88% yield with 1 in conc. sulfuric acid in 5 min at 20ºC, 1a) but in only 70% yield with NBS in 50% sulfuric acid in 3 h at 85ºC. Thus 1 has been widely used as an eff ective brominating reagent.3)
HN
N
N
O
OO
Br
Br
NO2
NO2
Br
N
Br
N
[D3753]
Example of iodinating products: 1,3-Diiodo-5,5’-dimethylhydantoin (DIH) (2), which was fi rst reported by Ozazi, is an useful iodinating reagent.4) 2 has higher reactivity and selectivity than molecular iodine or N-iodosuccinimide (NIS), which are frequently used for iodination reaction. 2 is a pale yellow solid that does not sublime like molecular iodine, and has low toxicity, which makes it easier to handle. In addition, dimethylhydantoin, which is formed after the reaction, can easily be removed by aqueous extraction.
2 reacts smoothly at room temperature with aromatic compounds in the presence of sulfuric acid to give the corresponding iodinated aromatic compounds in a high regioselectivity and a high yield. Moreover, even low-activated substances such as nitrobenzene can easily be iodinated by using sulfuric acid.5)
OMe
OMe 2 (0.5 eq.)
NO22 (1 eq.)
COOH 2 (1 eq.)
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Fluorination
B2440
Product No. Product Name Unit Size B2440 Bis(2-methoxyethyl)aminosulfur Trifl uoride 5g 25g B3664 4-tert-Butyl-2,6-dimethylphenylsulfur Trifl uoride (FLUOLEADTM) 5g D1868 (Diethylamino)sulfur Trifl uoride (DAST) 5g 25g 100g D3812 1,1'-Difl uoro-2,2'-bipyridinium Bis(tetrafl uoroborate) 1g F0335 N-Fluorobenzenesulfonimide (NFSI) 5g 25g F0358 N-Fluoro-N '-(chloromethyl)triethylenediamine Bis(tetrafl uoroborate) (F-TEDA-BF4) 5g 25g 100g F0344 1-Fluoro-2,6-dichloropyridinium Tetrafl uoroborate 5g 25g F0225 2-Fluoro-1-methylpyridinium p-Toluenesulfonate 5g 25g F0343 1-Fluoropyridinium Tetrafl uoroborate 5g 25g F0327 1-Fluoropyridinium Trifl uoromethanesulfonate 5g 25g F0346 1-Fluoro-2,4,6-trimethylpyridinium Tetrafl uoroborate 5g F0328 1-Fluoro-2,4,6-trimethylpyridinium Trifl uoromethanesulfonate 5g 25g H0598 Ishikawa's Reagent 25g 100g 500g M1573 Morpholinosulfur Trifl uoride (Morph-DAST) 1g 5g
Halogenation S yn th et ic O rg an ic C he m is try
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Product No. Product Name Unit Size P1758 Potassium Fluoride 300g P1888 Potassium Hydrogenfl uoride 500g P0999 Pyridinium Poly(hydrogenfl uoride) 25g 100g T1295 Tetrabutylammonium Bifl uoride 5g 25g T1909 Tetrabutylammonium Difl uorotriphenylsilicate 5g 25g T1592 Tetrabutylammonium Difl uorotriphenylstannate 1g 5g T1635 Tetrabutylammonium Dihydrogen Trifl uoride 5g 25g T1037 Tetrabutylammonium Fluoride Hydrate 25g 100g T1339 Tetrabutylammonium Fluoride (70-75% in Water) 25g 500g T1125 Tetrabutylammonium Fluoride (ca. 1mol/L in Tetrahydrofuran) 25mL 100mL T1338 Tetrabutylammonium Fluoride (ca. 1mol/L in Tetrahydrofuran) 25mL 100mL 500mL T2027 Tetraethylammonium Fluoride Tetrahydrofl uoride 10g T2026 Tetraethylammonium Fluoride Trihydrofl uoride 10g T2754 Tetramethylammonium Fluoride Tetrahydrate 5g 25g T2023 Triethylamine Pentahydrofl uoride 10g T2022 Triethylamine Trihydrofl uoride 10g
Chlorination
B1543
O
O
Product No. Product Name Unit Size B1543 Benzyltrimethylammonium Tetrachloroiodate 5g H0362 tert-Butyl Hypochlorite 25g 500g C0075 Chloramine B Hydrate 25g 500g C0076 Chloramine T Trihydrate 25g 500g C1374 o-Chloramine T 25g C0202 Chloromethyl Methyl Ether 25g 100g 500g
Halogenation S ynthetic O
rganic C hem istry
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Product No. Product Name Unit Size C0802 N-Chlorophthalimide 25g 500g C0291 N-Chlorosuccinimide 25g 100g 500g C0460 Cyanuric Chloride 25g 500g D0318 Dichloramine T 25g 500g D1645 Dichloromethyl Methyl Ether 25g 250g M0094 Methanesulfonyl Chloride 25g 500g M0970 Methoxyacetyl Chloride 25g 500g O0082 Oxalyl Chloride 25g 100g 500g D1003 Sodium Dichloroisocyanurate 25g 500g T2048 Thionyl Chloride (ca. 1mol/L in Dichloromethane) 500mL T2040 Thionyl Chloride 500mL T0620 Trichloroisocyanuric Acid 25g 500g T0611 Trichloromethanesulfonyl Chloride 5g 25g
Bromination
T1382
CH3
Br3
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Product No. Product Name Unit Size T1382 Benzyltrimethylammonium Tribromide 5g 25g B2358 Bis(2,4,6-trimethylpyridine)bromonium Hexafl uorophosphate 1g 5g B2553 Boron Tribromide (17% in Dichloromethane, ca. 1mol/L) 100mL B2414 Bromine 90g 500g B0530 N-Bromoacetamide 5g 25g B1016 2-Bromo-2-cyano-N,N-dimethylacetamide 5g B3311 Bromodimethylsulfonium Bromide 5g 25g B1697 N-Bromophthalimide 5g 25g B2152 N-Bromosaccharin 5g 25g B0656 N-Bromosuccinimide 25g 100g 500g B0662 Bromotrichloromethane 25g 500g B3596 1-Butyl-3-methylimidazolium Tribromide 5g D3976 1,8-Diazabicyclo[5.4.0]-7-undecene Hydrogen Tribromide 5g D1265 1,3-Dibromo-5,5-dimethylhydantoin 25g 500g D3753 Dibromoisocyanuric Acid 5g 25g D1710 5,5-Dibromomeldrum's Acid (=5,5-Dibromo-2,2-dimethyl-4,6-dioxy-1,3-dioxane) 5g 25g D1987 1,2-Dibromo-1,1,2,2-tetrachloroethane 25g D1787 4-Dimethylaminopyridinium Bromide Perbromide 5g 25g B2148 Monosodium Bromoisocyanurate Hydrate 25g P1743 Phosphorus Tribromide 300g P0825 Pyridinium Bromide Perbromide 25g 500g T1235 2,4,4,6-Tetrabromo-2,5-cyclohexadienone 5g 25g T1284 Tetrabutylammonium Tribromide 25g 100g 500g P0928 Trimethylphenylammonium Tribromide 25g 500g
Iodination
B1604
Halogenation S ynthetic O
rganic C hem istry
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Product No. Product Name Unit Size H1221 Hydriodic Acid (57%) 300mL I0604 Iodine 25g 500g I0784 N-Iodosaccharin 5g I0074 N-Iodosuccinimide 5g 25g 100g P2086 Pyridine Iodine Monochloride 1g 5g T2717 Tetramethylammonium Dichloroiodate 5g I0308 Trimethylsilyl Iodide (stabilized with Aluminum) 5g 25g
References 1) a) W. Gottardi, Monatsh. Chem. 1968, 99, 815; b) W. D. Brown, A. H. Gouliaev, Synthesis 2002, 83. 2) S. C. Virgil, in Encyclopedia of Reagents for Organic Synthesis, ed. by L. A. Paquette, John Wiley & Sons, Chichester,
2001, pp. 1560-1561. 3) a) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221; b) T. R. Walters, W. W. Zajac Jr., J. M. Woods, J. Org. Chem. 1991, 56, 316.
4) O. O. Orazi, R. A. Corral, H. E. Bertorello, J. Org. Chem. 1965, 30, 1101. 5) V. K. Chaikovskii, V. D. Filimonov, A. A. Funk, V. I. Skorokhodov, V. D. Ogorodnikov, Russ. J. Org. Chem. 2007, 43, 1291.
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Trifl uoromethylation
The size of a fluorine atom is similar to a hydrogen atom but the electric property of it is more electronegative. So, by replacing a hydrogen atom of substances with a fl uorine atom, their biological properties can be dramatically changed without a conformational change. Recently, the synthetic and biological studies of fl uorinated molecules have attracted a lot of interest in the fi elds of pharmaceuticals and agrochemicals research. Especially, the synthetic study of the trifluoromethyl group-containing compounds is now actively proceeding. As a method for direct trifluoromethylation, nucleophilic and electrophilic/radical fluorinating reactions are commonly used. Ruppert-Prakash reagent ((Trifluoromethyl)trimethylsilane) is the most popular nucleophilic trifl uoromethylating reagent and which readily reacts with a fl uoride ion to release the trifluoromethylanion species. This active species shows nucleophilicity and reacts with carbonyl compounds to proceed with the trifluoromethylation.1) Also, the nucleophilic trifluoromethylation of aromatic halides can be performed with the use of copper catalysts.2)
O
KF, NMP/DMF
CF3
X
[T1570]
[T2764]
The study of electrophilic trifluoromethylations has lagged compared to that of nucleophilic trifl uoromethylations. However, recently some reagents usable for electrophilic trifl uoromethylation have been reported. Shibata et al. have developed an electrophilic α-trifl uoromethylation of β-ketoesters using the fl uorinated Johnson reagent 1.3) The hypervalent iodine(III)CF3 reagents 2 and 3 developed by Togni et al. are widely used for trifl uoromethylations of thiols, alcohols, phosphines, and heteroarenes.4) Also, Baran et al. have reported the radical trifl uoromethylation of heteroarenes using the Langlois reagent or zinc(II) bis(trifl uoromethanesulfi nate) (Zn(SO2R)2) with tert-butyl hydroperoxide.5)
S N
rganic C hem istry
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Z0028
Zn2
Product No. Product Name Unit Size F0311 Methyl Difl uoro(fl uorosulfonyl)acetate 5g 25g O0367 [(Oxido)phenyl(trifl uoromethyl)-λ4-sulfanylidene]dimethylammonium Tetrafl uoroborate 200mg 1g P2172 (1,10-Phenanthroline)(trifl uoromethyl)(triphenylphosphine)copper(I) 1g 5g T1336 Sodium Trifl uoroacetate 25g 100g 500g T2033 Sodium Trifl uoromethanesulfi nate 5g 25g T2764 Triethyl(trifl uoromethyl)silane 1g 5g T3014 1-Trifl uoromethyl-1,2-benziodoxol-3(1H)-one (contains 60% Diatomaceous earth) 1g 5g T2624 1-Trifl uoromethyl-3,3-dimethyl-1,2-benziodoxole 1g 5g T1570 (Trifl uoromethyl)trimethylsilane 5g 25g T2883 (Trifl uoromethyl)tris(triphenylphosphine)copper(I) 1g 5g Z0028 Zinc(II) Bis(trifl uoromethanesulfi nate) Dihydrate 1g 5g
References 1) a) I. Ruppert, K. Schlich, W. Volbach, Tetrahedron Lett. 1984, 25, 2195. b) G. K. S. Prakash, R. Krishnamurti, G. A. Olah, J. Am. Chem. Soc. 1989, 111, 393.
2) M. Oishi, H. Kondo, H. Amii, Chem. Commun. 2009, 1909. 3) S. Noritake, N. Shibata, S. Nakamura, T. Toru, M. Shiro, Eur. J. Org. Chem. 2008, 3465. 4) a) P. Eisenberger, S. Gischig, A. Togni, Chem. Eur. J. 2006, 12, 2579. b) I. Kieltsch, P. Eisenberger, A. Togni, Angew. Chem. Int. Ed. 2007, 46, 754. c) P. Eisenberger, I. Kieltsch, N. Armanino, A. Togni, Chem. Commun. 2008, 1575. d) K. Stanek, R. Koller, A. Togni, J. Org. Chem. 2008, 73, 7678. e) P. Eisenberger, I. Kiltsch, R. Koller, K. Stanek, A. Togni, Org. Synth. 2011, 88, 168.
5) a) B. R. Langlois, E. Laurent, N. Roidot, Tetrahedron Lett. 1991, 32, 7525. b) Y. Ji, T. Bruecki, R. D. Baxter, Y. Fujiwara, I. B. Seiple, S. Su, D. G. Blackmond, P. S. Baran, Proc. Natl. Acad. Sci. USA
2011, 108, 14411. c) Y. Fujiwara, J. A. Dixon, R. A. Rodriguez, R. D. Baxter, D. D. Dixon, M. R. Collins, D. G. Blackmond, P. S. Baran, J. Am. Chem. Soc. 2012, 134, 1494.
d) Y. Fujiwara, J. A. Dixon, F. O'Hara, E. Daa Funder, D. D. Dixon, R. A. Rodriguez, R. D. Baxter, B. Herlé, N. Sach, M. R. Collins, Y. Ishihara, P. S. Baran, Nature 2012, 492, 95.
Trifl uoromethylation S yn th et ic O rg an ic C he m is try
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Trifl uoromethylthiolation
The trifl uoromethylthio group (CF3S) has attracted attention as a potentially-signifi cant functional group in the pharmaceutical and agrochemical fi elds because of its strong electron-withdrawing eff ect and high lipophilicity. Some methods for direct trifl uoromethylthiolation have been developed1-4) and one of them, copper(I) trifl uoromethanethiolate (CuSCF3) is an eff ective nucleophilic trifl uoromethylthiolating reagent. On the other hand, a simple electrophilic reagent, trifl uoromethylsulphenyl chloride (CF3SCl) is gaseous and highly toxic, so it is hardly used now. Recently, some electrophilic trifl uoromethylthiolating reagents which are safer to use and easier to
handle, have been reported. Both N-methyl-N-(trifl uoromethylthio)aniline1) developed by Billard et al. and N-(trifl uoromethylthio)phthalimide4) developed by Rueping are useful electrophilic trifl uoromethylthiolating reagents because their states are liquid and solid respectively. In addition, Shibata et al. have developed a hypervalent iodonium ylide having a trifl uoromethanesulfonyl group 3, and used it for the electrophilic trifl uoromethylthiolation. In this reaction, it seems that the trifl uoromethylthiocation species generated in situ by the reduction of 3 acts as an electrophilic trifl uoromethylthiolating reagent for enamines, indoles and β-ketoesters.3)
CH3
P2143
Product No. Product Name Unit Size P2143 Benzoyl(phenyliodonio)(trifl uoromethanesulfonyl)methanide 1g 5g C1159 Copper(I) Trifl uoromethanethiolate 1g 5g M2595 N-Methyl-N-(trifl uoromethylthio)aniline 200mg 1g T3143 N-(Trifl uoromethylthio)phthalimide 1g 5g
References 1) a) F. Baert, J. Colomb, T. Billard, Angew. Chem. Int. Ed. 2012, 51, 10382. b) A. Ferry, T. Billard, E. Bacqué, B. R. Langlois, J. Fluorine Chem. 2012, 134, 160. c) Y. Yang, X. Jiang, F.-L. Qing, J. Org. Chem. 2012, 77, 7538. d) A. Ferry, T. Billard, B. R. Langlois, E. Bacqué, Angew. Chem. Int. Ed. 2009, 48, 8551.
2) X. Shao, X. Wang, T. Yang, L. Lu, Q. Shen, Angew. Chem. Int. Ed. 2013, 52, 3457. 3) Y.-D. Yang, A. Azuma, E. Tokunaga, M. Yamasaki, M. Shiro, N. Shibata, J. Am. Chem. Soc. 2013, 135, 8782. 4) R. Pluta, P. Nikolaienko, M. Rueping, Angew. Chem. Int. Ed. 2014, 53, 1650.
Trifl uoromethylthiolation S ynthetic O
rganic C hem istry
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Formylation
Formyl group-containing compounds are important building blocks in organic synthesis since the formyl group can be transformed to other various functional groups. Aldehydes are the most typical formyl group- containing compound and are widely used as a substrate for carbon-carbon bond forming reactions such as the aldol reaction and the Wittig reaction.1-2) Also, their oxidation/reduction converts them to the related alcohols and carboxylic acids respectively, while the reductive amination is an effi cient functional transformation of the formyl group into amines.3-5) As above reactions,the formyl group is a versatile precursor of organosynthetic reactions and a number of various formyl group introducing reagents have been developed. Reagents for the formylation are classifi ed into three types according to their reactivity and substrates: (1) electrophilic aromatic substitution, (2) reaction with carbon nucleophiles, and (3) direct formylation at oxygen or nitrogen atoms.
(1) Electrophilic aromatic substitution
(also applicable to some electron-rich alkenes) [C1545] [H0093] [D1645]
Vilsmeier reagent is a strong electrophile and formylates electron-rich alkenes and aromatic rings by electrophilic aromatic substitution.6) This reagent is widely used and can be prepared by the reaction of DMF or N-methylformanilide with phosphoryl chloride.7) The Duff reaction using hexamethylenetetramine is eff ective to formylate electron-rich aromatic compounds such as phenols and indoles.8) Furthermore, the Riecke reaction using dichloromethyl methyl ether is suitable for formylation at the sterically hindered site of substances.9)
(2) Formylation by the reaction with carbon nucleophiles
formylating reagent
Formyl group-containing compounds can be also synthesized by the reaction of Grignard reagents or organolithium compounds with N,N-disubstituted formamides, orthoformates, N-methoxymethyleneaniline and so on (Bouveault/ Bodroux-Chichibabin aldehyde synthesis).10,11) In addition, it is known that the direct C-formylation of ketones can be performed by the reaction of related ketone enolates with TFEF.12)
(3) O/N-Formylation
[F0854] [F0356] [B3920]
N-Formylsaccharin, cyanomethyl formate,13-15) and 1-formyl-1H-benzotriazole work as O/N-formylating reagents, and successfully react with alcohols and amines under mild conditions to aff ord the desired O/N-formylated compounds. Especially, N-formylsaccharin can be used not only as a formylating reagent but also as a carbon monoxide introducing reagent (for more details, see the page 2.).
Formylation S yn th et ic O rg an ic C he m is try
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B3920
Formylation S ynthetic O
rganic C hem istry
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References 1) T. Mukaiyama, K. Narasaka, K. Banno, Chem. Lett. 1973, 1011. 2) S. G. Levine, J. Am. Chem. Soc. 1958, 80, 6150. 3) Seyden-Penne, “Reductions by Alumino- and Borohydrides in Organic Synthesis”, 2nd ed., Wiley-VCH, New York, 1997. 4) B. S. Bal, W. E. Childers Jr, H. W. Pinnick, Tetrahedron 1981, 37, 2091. 5) A. F. Abdel-Magid, K. G. Carson, B. D. Harris, C. A. Maryanoff , R. D. Shah, J. Org. Chem. 1996, 61, 3849. 6) a) Tasneem, Synlett 2003, 138. b) R. A. Aungst Jr, C. Chan, R. L. Funk, Org. Lett. 2001, 3, 2611. 7) A. Miyawaki, D. Kikuchi, M. Niki, Y. Manabe, M. Kanematsu, H. Yokoe, M. Yoshida, K. Shishido, J. Org. Chem. 2012, 77, 8231.
8) a) J. C. Duff , E. J. Bills, J. Chem. Soc. 1932, 1987. b) J. C. Duff , E. J. Bills, J. Chem. Soc. 1934, 1305. c) J. C. Duff , E. J. Bills, J. Chem. Soc. 1941, 547. d) J. C. Duff , E. J. Bills, J. Chem. Soc. 1945, 276. 9) A. Rieche, H. Gross, E. Höft, Chem. Ber. 1960, 93, 88. 10) L. I. Smith, M. Bayliss, J. Org. Chem. 1941, 6, 437. 11) L. I. Smith, J. Nichols, J. Org. Chem. 1941, 6, 489. 12) G. H. Zayia, Org. Lett. 1999, 1, 989. 13) T. Cochet, V. Bellosta, A. Greiner, D. Roche, J. Cossy, Synlett 2011, 1920. 14) J. Deutsch, H.-J. Niclas, Synth. Commun. 1993, 23, 1561. 15) G. Bélanger, J. Boudreault, F. Lévesque, Org. Lett. 2011, 13, 6204. 16) N. U. Hofsløkken, L. Skattebøl, Acta Chem. Scand. 1999, 53, 258. 17) V. V. Mezheritskii, M. S. Korobov, O. M. Golyanskaya, N. I. Omelichkin, L. G. Minyaeva, G. S. Borodkin, A. A. Milov, A. V. Tsukanov, A. D. Dubonosov, Russ. J. Org. Chem. 2012, 48, 241.
18) N. Akikusa, K. Mitsui, T. Sakamoto, Y. Kikugawa, Synthesis 1992, 1058. 19) D. Comins, A. I. Meyers, Synthesis 1978, 403.
Zincke Aldehyde Synthesis (introduction of 4-formyl-1,3-butadienyl group)
N H
N H
N SiMe3
N SiMe3
CHO H
Y. 67%
Y. 84%
NH CHO
N H
1-(2,4-Dinitrophenyl)pyridinium chloride (Zincke salt, 1) reacts with secondary amines to aff ord the corresponding 5-amino-2,4-pentadienals (Zinke aldehydes).1) This type of reaction has been applied to the synthesis of various indole alkaloids.2) For example, Vanderwal et al. have reported the total synthesis of norfl uorocurarine, a Strychnos alkaloid.3)
1) T. Zincke, W. Wurker, Liebigs Ann. Chem. 1905, 338, 107. 2) D. B. C. Martin, L. Q. Nguyen, C. D. Vanderwal, J. Org. Chem. 2012, 77, 17. 3) D. B. C. Martin, C. D. Vanderwal, J. Am. Chem. Soc. 2009, 131, 3472.
Formylation S yn th et ic O rg an ic C he m is try
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Cyanation
A cyano group is a strong electron withdrawing group and a number of cyanating reagents are widely used in organic synthesis. The cyano group is converted to other functional groups such as carboxylic acids or amides by hydrolysis, and is also converted to amines or aldehydes by reduction with some reducing reagents. Furthermore, alkyl nitriles which are typical cyano group containing compounds are transformed into related ketones by reaction with carbon nucleophilic agents such as Grignard reagents or organolithium reagents. This synthetic method is effi cient to synthesize the asymmetric ketones. On the other hand, the cyano group can be used for cycloaddition reactions with other multiple bonds. For instance, alkyl nitriles are additionally cyclized with azides to give the tetrazoles. As introducing methods for the cyano group, the reaction of potassium cyanide with alkyl halides is a typical synthetic method and the copper cyanide-mediated Sandmeyer reaction and the Rosenmund- von Braun reaction have been known for a long time. Recently, cyanation reactions using palladium catalysts with some cyanating reagents have been developed. In addition, benzyl thiocyanate1), ethyl cyanoacetate2), tert-butyl isocyanide3) and acetone cyanohydrin4) play as cyanide ion sources and can be used for the direct cyanation of various substances.
CH2SCN
[T0198]
S CO2CuCuTC =
X
R
Cyanation S ynthetic O
rganic C hem istry
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M0361
CH3
CH3
CH3
Product No. Product Name Unit Size M0361 Acetone Cyanohydrin 25mL 500mL T0198 Benzyl Thiocyanate 25g 500g B1274 tert-Butyl Isocyanide 5mL 25mL C3003 2-Chlorobenzyl Thiocyanate 1g 5g C1952 Copper(I) Cyanide 25g 300g C1242 Diethyl Cyanophosphonate 5g 25g C0441 Ethyl Cyanoacetate 25g 500g P1613 Potassium Cyanide 25g T1046 p-Toluenesulfonylmethyl Isocyanide 5g 25g T0990 Trimethylsilyl Cyanide 25mL 100mL 500mL
References 1) Z. Zhang, L. S. Liebeskind, Org. Lett. 2006, 8, 4331. 2) S. Zheng, C. Yu, Z. Shen, Org. Lett. 2012, 14, 3644. 3) J. Peng, J. Zhao, Z. Hu, D. Liang, J. Huang, Q. Zhu, Org. Lett. 2012, 14, 4966. 4) K. J. Powell, L.-C. Han, P. Sharma, J. E. Moses, Org. Lett. 2014, 16, 2158.
Cyanation S yn th et ic O rg an ic C he m is try
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Amination
The Gabriel reagent is widely used as a nucleophilic aminating agent since its reactivity is reliable and its handling is easy.1) A variety of aminating agents analogous to the Gabriel reagent have been reported. The potassium salt of imide 1 reacts with alkyl halide to give imide 2. 2 is treated with base or acid to give either N-Boc-amine 3 or N-methoxycarbonylamine 4, respectively. Moreover, 1 also serves as an acid nucleophile in the Mitsunobu reaction to allow for the conversion of hydroxy groups to amino groups. Therefore, 1 is a useful reagent to give monoprotected amines.2)
1 [I0510]
,
Fukuyama and co-workers have demonstrated various reactions using the N-substituted sulfonamide 5.3) Smooth reactions of 5 occur with alkyl halides under basic conditions and alcohols under Mitsunobu conditions to provide o-nitrobenzenesulfonyl (o-Ns) amines 6. The various o-Ns amines (Alloc, Boc, Cbz) 6 obtained from these reactions can be selectively deprotected, under the appropriate conditions, to aff ord the monoprotected amines 7 and 8. Furthermore, 7 can be converted to the primary amine in high yields via a second deprotection. 8 can be converted to the secondary amine in high yields by repeating the alkylation and deprotection process.4)
5 6
R1OH, DEAD, PPh3
Alloc 5a [A1632] Boc 5b [B2303] Cbz 5c [C1757]
or or
R1NHY R1NH2
R1NHR2
On the other hand, acetoxime O-(2,4,6-trimethylphenyl)sulfonate 9 has been reported as a useful electrophilic aminating agent. 9 reacts with Grignard reagents in the presence of a catalytic amount of magnesium chloride to aff ord primary amines in good yields.5)
9 [A1441] R MgBr C
Me
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Amination
B3380
O
Product No. Product Name Unit Size A1441 Acetoxime O-(2,4,6-Trimethylphenylsulfonate) 5g 25g A1632 N-Allyloxycarbonyl-2-nitrobenzenesulfonamide 5g A1137 4-Amino-1,2,4-triazole 25g 250g A2457 2-Azido-1,3-dimethylimidazolinium Hexafl uorophosphate 5g A1341 Azidomethyl Phenyl Sulfi de 5g B3380 2-Bromoisobutyramide 5g 25g B2303 N-(tert-Butoxycarbonyl)-2-nitrobenzenesulfonamide 1g 5g 25g B1648 N-(tert-Butoxycarbonyl)-p-toluenesulfonamide 10g 25g B2857 tert-Butyl [Bis(4-methoxyphenyl)phosphinyloxy]carbamate 1g 5g I0510 tert-Butyl Methyl Iminodicarboxylate 5g C1757 N-Carbobenzoxy-2-nitrobenzenesulfonamide 5g 25g I0497 Di-tert-butyl Iminodicarboxylate 5g 25g B1734 Diethyl N-(tert-Butoxycarbonyl)phosphoramidate 5g D2361 Diethyl Phosphoramidate 25g D1899 N,O-Dimethylhydroxylamine Hydrochloride 25g 100g 500g D1672 Diphenylphosphoryl Azide 5g 25g 250g M1182 Ethyl O-Mesitylsulfonylacetohydroxamate 1g 5g 25g H0093 Hexamethylenetetramine 25g 500g H0258 Hydroxylamine Hydrochloride 25g 500g H0196 Hydroxylamine Sulfate 25g 500g H0530 Hydroxylamine-O-sulfonic Acid 25g 100g 500g M0886 O-Methylhydroxylamine Hydrochloride (ca. 40% in Water, ca. 5.4mol/L) 25mL 500mL M0343 O-Methylhydroxylamine Hydrochloride 25g 100g 500g P1235 Phthalimide DBU Salt 25g
S yn th et ic O rg an ic C he m is try
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Product No. Product Name Unit Size P0403 Phthalimide Potassium Salt 25g 500g D2479 Sodium Diformylamide 25g T1184 Trimethylsilylmethyl Azide 1g 5g
References 1) S. Gabriel, Ber. 1887, 20, 2224; M. S. Gibson, R. W. Bradshaw, Angew. Chem. Int. Ed. Engl. 1968, 7, 919; U. Ragnarsson, L. Grehn, Acc. Chem. Res. 1991, 24, 285.
2) J. D. Elliott, J. H. Jones, J. Chem. Soc., Chem. Commun. 1977, 758; C. T. Clarke, J. D. Elliott, J. H. Jones, J. Chem. Soc., Perkin Trans. 1 1978, 1088; J. M. Chong, S. B. Park, J. Org. Chem. 1993, 58, 7300.
3) T. Fukuyama, M. Cheung, T. Kan, Synlett 1999, 1301. 4) T. Kan, A. Fujiwara, H. Kobayashi, T. Fukuyama, Tetrahedron 2002, 58, 6267. 5) E. Erdik, M. Ay, Synth. React. Inorg. Met.-Org. Chem. 1989, 19, 663.
Amination S ynthetic O
rganic C hem istry
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34 Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.
Mitsunobu Reaction
O +
OR1
R2
R3
O
The Mitsunobu reaction is a unique dehydration-condensation reaction of alcohols with various organic acids, which together with azodicarboxylate esters and triphenylphosphine are generally used as dehydration-condensation reagents.1) The Mitsunobu reaction is carried out under mild conditions and alcohols with a chiral center are inverted with the Walden-inversion. Acid components such as carboxylic acids, phenols, active methylene compounds and imides are applicable for this transformation. Therefore, the Mitsunobu reaction is one of the most useful synthetic methods in organic synthesis.
R1 R2
SHR
O
Also, synthetic applications of the Mitsunobu reaction have been widely studied due to its excellent chemical reactivity and various improved synthetic methods have been reported as follows.2)
1) The basicity of the azodicarboxyamide derivatives is higher compared to that of azodicarboxylate esters, and its chemical property expands the availability of the acids into weaker acids with high pKa value. In addition, after the reactions, these reagents can be easily removed by column chromatography or extraction because they are high-polarity molecules.3)
N NC C
[A0705]
[A1458]
[A1051]
Mitsunobu Reaction S yn th et ic O rg an ic C he m is try
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2) By using phosphines with a base moiety4) or diphenylphosphinopolystyrene resins5) instead of triphenylphosphine, the generated phosphine oxides can be easily removed. In addition, phenoxydiphenylphosphine is an eff ective agent when sterically hindered tertiary alcohols are employed.6)
P Ph
PO Ph
Ph
3) Tsunoda et al. have reported that cyanomethylene tributyl phosphorane is an effective agent for improving the Mitsunobu reaction.7) It plays roles of both azodicarboxylate esters and tributylphosphine independently, and enables the Mitsunobu reaction to proceed even when using nucleophiles such as active methylene compounds with high pKa values as well as typical organic acids. However, it is necessary to pay attention when this reagent is used with ketones or aldehydes because it behaves like a Wittig reagent.8)
[C1500]
O O NC SO2Ph MeS SO2Tol
pKa = 13.3 pKa = 12.0 pKa = 23.4
4) It has been reported that the stoichiometry used for the amounts of azodicarboxylate esters can be reduced to catalytic amounts of one by using iodobenzene diacetate or iron phthalocyanine as a reoxidant.9) This method can reduce the hydrazide by-product to a minimum.
Azodicarboxylates & Amides
O O
rganic C hem istry
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Product No. Product Name Unit Size A1458 1,1'-Azobis(N,N-dimethylformamide) 1g 5g A1051 1,1'-(Azodicarbonyl)dipiperidine 5g 25g B3364 Bis(2-methoxyethyl) Azodicarboxylate 5g A1332 Bis(2,2,2-trichloroethyl) Azodicarboxylate 5g A0776 Dibenzyl Azodicarboxylate (40% in Dichloromethane, ca. 1.7mol/L) 25g D3544 Di-tert-butyl Azodicarboxylate (20% in Toluene) 25g A0705 Diethyl Azodicarboxylate (40% in Toluene, ca. 2.2mol/L) 25g 100g 250g A1246 Diisopropyl Azodicarboxylate (40% in Toluene, ca. 1.9mol/L) 25g 100g 250g A0882 Dimethyl Azodicarboxylate (40% in Toluene, ca. 2.7mol/L) 25g
Phosphines (Mitsunobu Reaction)
Modifi ed New Mitsunobu Reaction (Tsunoda Reagent)
C1500
P
Bu
Bu
CN
Mitsunobu Reaction S yn th et ic O rg an ic C he m is try
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Product No. Product Name Unit Size C1500 Cyanomethylenetributylphosphorane 1g 5g 25g
References 1) O. Mitsunobu, Synthesis 1981, 1. 2) T. Onozawa, TCIMAIL 1999, number 104, 10. 3) a) T. Tsunoda, Y. Yamamiya, S. Ito, Tetrahedron Lett. 1993, 34, 1639. b) T. Tsunoda, J. Otsuka, Y. Yamamiya, S. Ito, Chem. Lett. 1994, 539. c) S. Ito, T. Tsunoda, Pure & Appl. Chem. 1994, 66, 2071. d) T. Tsunoda, Y. Yamamiya, Y. Kawamura, S. Ito, Tetrahedron Lett. 1995, 36, 2529.
4) a) L. D. Arnold, H. I. Assil, J. C. Vederas, J. Am. Chem. Soc. 1989, 111, 3973. b) A. R. Tunoori, D. Dutta, G. I. Georg, Tetrahedron Lett. 1998, 39, 8751.
5) R. A. Amos, R. W. Emblidge, N. Havens, J. Org. Chem. 1983, 48, 3598. 6) Review: T. Mukaiyama, K. Kuroda, Y. Maruyama, Heterocycles 2010, 80, 63. 7) T. Tsunoda, M. Nagaku, C. Nagino, Y. Kawamura, F. Ozaki, H. Hioki, S. Ito, Tetrahedron Lett. 1995, 36, 2531. 8) T. Tsunoda, H. Takagi, D. Takaba, H. Kaku, S. Ito, Tetrahedron Lett. 2000, 41, 235. 9) a) T. Y. S. But, P. H. Toy, J. Am. Chem. Soc. 2006, 128, 9636. b) D. Hirose, T. Taniguchi, H. Ishibashi. Angew. Chem. Int. Ed. 2013, 52, 4613.
Mitsunobu Reaction S ynthetic O
rganic C hem istry
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Condensation & Active Esterifi cation
The synthesis of carboxylic esters is one of the most fundamental and important processes for producing useful compounds in organic chemistry. The classical esterifi cation reaction is condensation of a carboxylic acid and an alcohol under acidic conditions. This is an equilibrium reaction, and in order to eff ectively generate the ester, the equilibrium need to be shift toward the ester. To achieve this equilibrium shift requires adding one of the substrates in large excess and the removal of the generated water by distillation. However, when both carboxylic acid and alcohol are expensive and not easily available, it is not economical to use one of the substrates in large excess. Thus the classical esterifi cation method is not the best method to use in such a case. Furthermore, when the substrate is unstable to heat, the classical method does not always yield the desired results. Since esterifi cation is a basic reaction that is applied to many diff erent types of substrates, there is a need for alternative methods which proceed under mild conditions without the need for using large excess of one of the substrates. Over the years, there has been much research done by many chemists, and many useful methods have been reported.
R2OH+ + Et3N (1.1 eq.), DMAP (0.1 eq.), rt
(1.1 eq.)(1.0 eq.)
95 98 >200 92
PhCH2 >200 Ph(CH2)2 THPO(CH2)5
O
OO
Me
NO2
Me
NO2
NO2
Me
OR2
O
R1COOH R2OH
CH2=CHCH2
Shiina and co-workers have reported a method using 2-methyl-6-nitrobenzoic anhydride (1). This esterifi cation procedure is quite simple. Triethylamine, a catalytic amount of 4-dimethylaminopyridine, and 1 were dissolved in a solvent. The carboxylic acid was added and stirred, and fi nally a nearly equimolar amount of alcohol was added and the reaction stirred under room temperature. Through this reaction process, the desired ester (ester A) is obtained in high yields. The nitro group on the condensation reagent 1 promotes and facilitates the esterifi cation under room temperature. The introduction of substituents at the two ortho positions of benzene ring controls the generation of byproduct (ester B). These two eff ects synergistically act to produce the desired ester in excellent yield and high purity. This reaction can also be applied to intramolecular esterifi cation, and can aff ord lactones in high yields.
A1797
F F
Condensation & Active Esterifi cation S yn th et ic O rg an ic C he m is try
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B3817
PF6
N
rganic C hem istry
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D3683
S
D1662
O
N
P0939
N
N
Q0016
N
SO2Cl
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S0836
OH
F
F
SO3Na
F
F
T1562
SO2Cl
CH3
CH3
CH3
CH3
SO2Cl
T2908
B(OH)2
N
Anhydride) 200mg 1g C1298 N-(2-Bromobenzyloxycarbonyloxy)succinimide 10g B1036 2-Bromo-1-ethylpyridinium Tetrafl uoroborate 5g 25g B2680 Bromotripyrrolidinophosphonium Hexafl uorophosphate 5g 25g B0832 N-tert-Butyl-5-methylisoxazolium Perchlorate 1g 5g C1574 tert-Butyl 2,4,5-Trichlorophenyl Carbonate 5g C1124 N-Carbobenzoxyoxysuccinimide 25g 250g C1362 2,2'-Carbonylbis(3,5-dioxo-4-methyl-1,2,4-oxadiazolidine) 5g C0119 1,1'-Carbonyldiimidazole 25g 250g C1988 O-(6-Chlorobenzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Hexafl uorophosphate 1g 5g C1926 O-(6-Chlorobenzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Tetrafl uoroborate 5g 25g C1131 N-(2-Chlorobenzyloxycarbonyloxy)succinimide 10g C1639 2-Chloro-1,3-dimethylimidazolinium Chloride (ca. 25% in Dichloromethane) 25g C1408 2-Chloro-1,3-dimethylimidazolinium Chloride 5g 25g C1651 2-Chloro-1,3-dimethylimidazolinium Hexafl uorophosphate 5g 25g C0905 2-Chloro-3-ethylbenzoxazolium Tetrafl uoroborate 5g 25g C0903 2-Chloro-1-methylpyridinium Iodide 25g C0906 2-Chloro-1-methylpyridinium p-Toluenesulfonate 25g C1379 1-(Chloro-1-pyrrolidinylmethylene)pyrrolidinium Hexafl uorophosphate 5g 25g C1375 1-(Chloro-1-pyrrolidinylmethylene)pyrrolidinium Tetrafl uoroborate 5g C1957 Chloro-N,N,N ',N '-tetramethylformamidinium Hexafl uorophosphate 1g 5g C2551 Chlorotripyrrolidinophosphonium Hexafl uorophosphate 5g 25g C2733 (1-Cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylaminomorpholinocarbenium
Hexafl uorophosphate (This product is only available in Japan.) 5g C1500 Cyanomethylenetributylphosphorane 1g 5g 25g C0793 1-Cyclohexyl-3-(2-morpholinoethyl)carbodiimide Metho-p-toluenesulfonate 5g 25g D0436 N,N '-Dicyclohexylcarbodiimide 25g 400g D3262 3-(Diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one 5g C1242 Diethyl Cyanophosphonate 5g 25g D2039 3,4-Dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine 10g 25g
Condensation & Active Esterifi cation S ynthetic O
rganic C hem istry
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Product No. Product Name Unit Size D3263 O-(3,4-Dihydro-4-oxo-1,2,3-benzotriazin-3-yl)-N,N,N ',N '-tetramethyluronium
Tetrafl uoroborate 5g 25g D1393 3,4-Dihydro-2H-pyrido[1,2-a]pyrimidin-2-one 5g 25g D0254 N,N '-Diisopropylcarbodiimide 25g 250g D3293 Dimesitylammonium Pentafl uorobenzenesulfonate 1g 5g D2919 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium Chloride 5g 25g D4029 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide 5g 25g D1601 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Hydrochloride 5g 25g 250g D1450 4-Dimethylaminopyridine 25g 100g 500g D2898 (4R,5R)-1,3-Dimethyl-4,5-diphenyl-2-[(S)-1-benzyl-2-hydroxyethylimino]imidazolidine 100mg D2899 (4S,5S)-1,3-Dimethyl-4,5-diphenyl-2-[(R)-1-benzyl-2-hydroxyethylimino]imidazolidine 100mg D1771 2,6-Dimethylpyridinium p-Toluenesulfonate 25g D3683 Diphenylammonium Trifl uoromethanesulfonate 1g 5g 25g D2038 Diphenyl (2,3-Dihydro-2-thioxo-3-benzoxazolyl)phosphonate 5g 25g D1720 N,N-Diphenyl-4-methoxybenzamide 5g D1672 Diphenylphosphoryl Azide 5g 25g 250g D2201 4,6-Diphenylthieno[3,4-d]-1,3-dioxol-2-one 5,5-Dioxide 5g C1407 Di-2-pyridyl Carbonate 5g D1114 2,2'-Dipyridyl Disulfi de 5g 25g 250g D2477 4,4'-Dipyridyl Disulfi de 5g 25g T1906 O,O '-Di-2-pyridyl Thiocarbonate 1g D1662 Di(N-succinimidyl) Carbonate 5g 25g D2222 2,2'-Dithiobis(5-nitropyridine) 5g E0916 O-[(Ethoxycarbonyl)cyanomethyleneamino]-N,N,N ',N '-tetramethyluronium Tetrafl uoroborate 1g 5g E0363 1-Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline 25g E0847 Ethyl Cyano(hydroxyimino)acetate 25g F0239 N-[(9H-Fluoren-9-ylmethoxy)carbonyloxy]succinimide 5g 25g F0225 2-Fluoro-1-methylpyridinium p-Toluenesulfonate 5g 25g F0726 Fluoro-N,N,N ',N '-tetramethylformamidinium Hexafl uorophosphate 1g 5g H0468 1-Hydroxybenzotriazole Monohydrate 25g 200g 500g H0528 N-Hydroxy-5-norbornene-2,3-dicarboximide 25g 250g H0395 N-Hydroxyphthalimide 25g 100g 500g B0249 N-Hydroxysuccinimide 25g H0623 N-Hydroxysuccinimide 25g 100g 500g H1304 N-Hydroxysulfosuccinimide Sodium Salt 200mg 1g M1186 2,4-Mesitylenedisulfonyl Dichloride 5g 25g M0071 2-Mesitylenesulfonyl Chloride 25g 500g M0670 9-Methyl-3,4-dihydro-2H-pyrido[1,2-a]pyrimidin-2-one 25g M1439 2-Methyl-6-nitrobenzoic Anhydride 1g 5g 25g M1116 6-Methyl-2H-pyrido[1,2-a]pyrimidin-2-one 5g T0681 4-Nitrophenyl Trifl uoroacetate 5g 25g N0477 3-Nitro-1,2,4-triazole 5g N0634 2-(5-Norbornene-2,3-dicarboximido)-1,1,3,3-tetramethyluronium Tetrafl uoroborate 5g 25g O0200 1,1'-Oxalyldiimidazole 1g 5g O0390 O-[2-Oxo-1(2H)-pyridyl]-N,N,N ',N '-tetramethyluronium Tetrafl uoroborate 1g 5g T0648 Pentachlorophenyl Trichloroacetate 25g P1626 Pentafl uoroanilinium Trifl uoromethanesulfonate 1g 5g 25g P2231 Pentafl uorophenyl 4-Nitrobenzenesulfonate 1g 5g P1042 Phosphorus Pentoxide - Methanesulfonic Acid 25g 500g P1320 Propylphosphonic Acid Anhydride (Cyclic Trimer) (48% in N,N-Dimethylformamide, ca. 1.6mol/L) 25g P1319 Propylphosphonic Acid Anhydride (Cyclic Trimer) (50% in Ethyl Acetate, ca. 1.7mol/L) 25g 100g P1768 3-Pyridinecarboxylic Anhydride 1g 5g P0939 4-Pyrrolidinopyridine 5g 25g Q0016 Quinoline-8-sulfonyl Chloride 5g 25g S0836 Sodium 2,3,5,6-Tetrafl uoro-4-hydroxybenzenesulfonate 1g 5g T1562 2,4,5,6-Tetramethylbenzenedisulfonyl Dichloride 5g T2908 2-[(2,2,6,6-Tetramethyl-1-piperidyl)methyl]phenylboronic Acid (contains varying amounts of Anhydride) 1g T2929 N,N,N ',N '-Tetramethyl-O-(N-succinimidyl)uronium Hexafl uorophosphate 5g 25g T2224 N,N,N ',N '-Tetramethyl-O-(N-succinimidyl)uronium Tetrafl uoroborate 1g 5g T1017 1H-Tetrazole 5g 25g T1985 1-(p-Toluenesulfonyl)imidazole 5g 25g T0340 1,2,4-Triazole 25g 100g 500g T1413 2,4,6-Trichlorobenzoyl Chloride 5g 25g T0389 2,4,5-Trichlorophenol 25g 500g T1593 4-Trifl uoromethylbenzoic Anhydride 10g T0459 2,4,6-Triisopropylbenzenesulfonyl Chloride 25g 500g T1122 2,4,6-Trimethylpyridinium p-Toluenesulfonate 25g
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References 1) I. Shiina, R. Ibuka, M. Kubota, Chem. Lett. 2002, 286. 2) I. Shiina, M. Kubota, R. Ibuka, Tetrahedron Lett. 2002, 43, 7535. 3) J. Tian, N. Yamagiwa, S. Matsunaga, M. Shibasaki, Org. Lett. 2003, 5, 3021. 4) I. Shiina, H. Oshiumi, M. Hashizume, Y. Yamai, R. Ibuka, Tetrahedron Lett. 2004, 45, 543. 5) I. Shiina, M. Kubota, H. Oshiumi, M. Hashizume, J. Org. Chem. 2004, 69, 1822. 6) I. Shiina, Chem. Rev. 2007, 107, 239. 7) Tokyo Kasei Kogyo Co., Ltd., Jpn. Kokai Tokkyo Koho 2003 335731, 2003.
Condensation & Active Esterifi cation S ynthetic O
rganic C hem istry
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Carbonyl Olefi nation
Carbonyl olefi nation is one of the most fundamental conversions in organic synthesis and a variety of synthetic methods have been developed. Particularly, synthetic methods focused on the chemical properties of heavy-atoms such as phosphorus, silicon and sulfur atoms had long been studied. One of them, the Wittig reaction is the representative carbonyl olefi nation reaction. Other similar reactions, the silicon-mediated Peterson olefi nation and two sulfur-based “Julia” carbonyl olefi nations named the Julia- Lythgoe olefi nation and the JuliaKocienski olefi nation are also useful olefi nating methods. Among them, as the Wittig and Horner-Emmons reactions are the most general carbonyl olefinations, a number of improved synthetic applications have also been investigated. Some of them allow providing easer work-up procedures and increasing the stereoselectivity of the double bond of olefi ns. They are even now widely used for this transformation.
SO2ArR4
R3
Aldehyde, Ketone
In the 1990s, organotitanium species-promoted carbonyl olefi nations had been studied and various successful methods were reported. The biggest advantage of the use of organotitanium species in carbonyl olefination is that not only aldehydes and ketones, but also esters and lactones can be transformed to the corresponding olefi ns. Furthermore, the basicities of the organotitanium species are weaker compared to that of Wittig type bases and these chemical properties enable easily enolizable substrates to be used in carbonyl olefi nations and to produce the desired olefi ns with high yields.
R1 R2
Br
Carbonyl Olefi nation S yn th et ic O rg an ic C he m is try
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A1012
rganic C hem istry
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T1458
Cl
CH3
CH3
T2001
Product No. Product Name Unit Size A1305 Acetonyltriphenylphosphonium Chloride 25g A1439 (Acetylmethylene)triphenylphosphorane 25g A1007 Allyltriphenylphosphonium Bromide 25g A1012 Allyltriphenylphosphonium Chloride 25g A0862 Amyltriphenylphosphonium Bromide 25g B2025 Benzyltriphenylphosphonium Bromide 25g 250g B0824 Benzyltriphenylphosphonium Chloride 25g 500g B1206 (Bromomethyl)triphenylphosphonium Bromide 5g 25g B1208 3-Bromopropyltriphenylphosphonium Bromide 25g B3928 (tert-Butoxycarbonylmethyl)triphenylphosphonium Bromide 25g B0970 Butyltriphenylphosphonium Bromide 25g 250g C1061 4-(Carboxybutyl)triphenylphosphonium Bromide 25g 250g C1759 (2-Chlorobenzyl)triphenylphosphonium Chloride 25g C1009 (Chloromethyl)triphenylphosphonium Chloride 5g 25g C1286 Cinnamyltriphenylphosphonium Bromide 25g C1739 (Cyanomethyl)triphenylphosphonium Chloride 25g 100g C1378 Cyclopropyltriphenylphosphonium Bromide 5g D2907 (2,4-Dichlorobenzyl)triphenylphosphonium Chloride 25g D4072 (3,4-Dimethoxybenzyl)triphenylphosphonium Bromide 5g D1654 2-Dimethylaminoethyltriphenylphosphonium Bromide 5g 25g D1655 2-(1,3-Dioxan-2-yl)ethyltriphenylphosphonium Bromide 5g 25g D2056 2-(1,3-Dioxolan-2-yl)ethyltriphenylphosphonium Bromide 5g 25g D2164 (1,3-Dioxolan-2-yl)methyltriphenylphosphonium Bromide 5g 25g E0421 4-Ethoxybenzyltriphenylphosphonium Bromide 5g E0407 Ethoxycarbonylmethyl(triphenyl)phosphonium Bromide 25g 250g E0382 Ethyltriphenylphosphonium Bromide 25g 500g E0549 Ethyltriphenylphosphonium Iodide 25g 250g T1944 Ethyl (Triphenylphosphoranylidene)acetate 25g 250g C1641 Ethyl 2-(Triphenylphosphoranylidene)propionate 5g F0331 (Formylmethyl)triphenylphosphonium Chloride 25g H0545 Heptyltriphenylphosphonium Bromide 25g 500g H0540 Hexyltriphenylphosphonium Bromide 25g 500g H1240 (2-Hydroxybenzyl)triphenylphosphonium Bromide 5g 25g I0552 Isopropyltriphenylphosphonium Iodide 5g 25g M1326 Methoxycarbonylmethyl(triphenyl)phosphonium Bromide 25g M0828 (Methoxymethyl)triphenylphosphonium Chloride 25g 100g 500g M0779 Methyltriphenylphosphonium Bromide 25g 100g 500g M0253 Methyltriphenylphosphonium Iodide 25g 100g 500g T1363 Methyl (Triphenylphosphoranylidene)acetate 25g 100g N0700 (1-Naphthylmethyl)triphenylphosphonium Chloride 5g 25g
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Product No. Product Name Unit Size N0701 (4-Nitrobenzyl)triphenylphosphonium Bromide 25g P1182 Phenacyltriphenylphosphonium Bromide 25g T2718 Tributyl(1,3-dioxolan-2-ylmethyl)phosphonium Bromide 5g T1458 2-(Trimethylsilyl)ethoxymethyltriphenylphosphonium Chloride 5g 25g T1510 (2-Trimethylsilylethyl)triphenylphosphonium Iodide 5g T1498 (3-Trimethylsilyl-2-propynyl)triphenylphosphonium Bromide 1g 5g T2001 (Triphenylphosphoranylidene)acetaldehyde 5g 25g T1958 (Triphenylphosphoranylidene)acetonitrile 5g 25g T2002 2-(Triphenylphosphoranylidene)acetophenone 5g T2565 (Triphenylphosphoranylidene)ketene 1g 5g P1438 Triphenylpropargylphosphonium Bromide 5g 25g P1200 Triphenylpropylphosphonium Bromide 25g 500g T1506 Triphenyl(tetradecyl)phosphonium Bromide 25g T1644 Triphenylvinylphosphonium Bromide 5g
Horner-Emmons Reaction
O
OCH2CH3
CH3CH2O
O
CH3CH2O
B4011
rganic C hem istry
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D3327
CH2
CH3
P
Product No. Product Name Unit Size B2815 Benzyl Dimethylphosphonoacetate 1g 5g B2801 9,10-Bis(diethylphosphonomethyl)anthracene 1g 5g B1923 4,4'-Bis(diethylphosphonomethyl)biphenyl 1g 5g B1714 Bis(2,2,2-trifl uoroethyl) (Methoxycarbonylmethyl)-phosphonate 1g 5g 25g B4011 N-(tert-Butoxycarbonyl)-2-phosphonoglycine Trimethyl Ester 1g 5g B2814 tert-Butyl Diethylphosphonoacetate 1g 5g C2440 N-Carbobenzoxy-2-phosphonoglycine Trimethyl Ester 1g 5g D3069 Diethyl Allylphosphonate 1g 5g B1795 Diethyl Benzylphosphonate 25g D3688 Diethyl (4-Bromobenzyl)phosphonate 5g 25g B1781 Diethyl 2-Bromoethylphosphonate 5g 25g D4434 Diethyl (3-Bromopropyl)phosphonate 1g 5g C1595 Diethyl (3-Chlorobenzyl)phosphonate 1g 5g D3335 Diethyl (4-Chlorobenzyl)phosphonate 5g 25g
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Product No. Product Name Unit Size D4588 Diethyl (Chloromethyl)phosphonate 1g 5g D3323 Diethyl (4-Cyanobenzyl)phosphonate 5g 25g C1430 Diethyl Cyanomethylphosphonate 5g 25g D2423 Diethyl 2,2-Diethoxyethylphosphonate 5g 25g D4074 Diethyl (1,3-Dithian-2-yl)phosphonate 5g E0483 Diethyl Ethylphosphonate 25g D3324 Diethyl (4-Fluorobenzyl)phosphonate 5g 25g D3689 Diethyl (4-Iodobenzyl)phosphonate 5g 25g D3325 Diethyl (4-Isopropylbenzyl)phosphonate 5g D3326 Diethyl (3-Methoxybenzyl)phosphonate 5g 25g D4000 Diethyl (4-Methoxybenzyl)phosphonate 5g 25g D3708 Diethyl (N-Methoxy-N-methylcarbamoylmethyl)phosphonate 1g 5g D3873 Diethyl (Methoxymethyl)phosphonate 5g 25g D3327 Diethyl (2-Methylbenzyl)phosphonate 5g 25g D3328 Diethyl (3-Methylbenzyl)phosphonate 5g 25g D3336 Diethyl (4-Methylbenzyl)phosphonate 5g 25g D3827 Diethyl Methylphosphonate 5g 25g M1208 Diethyl (Methylthiomethyl)phosphonate 5g 25g D3339 Diethyl (2-Oxo-2-phenylethyl)phosphonate 1g 5g D3174 Diethyl (2-Oxopropyl)phosphonate 5g 25g P1193 Diethyl (Phthalimidomethyl)phosphonate 5g 25g P1258 Diethyl 1-Pyrrolidinemethylphosphonate 5g D4607 Diethyl (Trichloromethyl)phosphonate 5g 25g D3992 Dimethyl 1,3-Benzodithiol-2-ylphosphonate 1g D3981 Dimethyl 2-(1,3-Dithiole)phosphonate 1g 5g M0943 Dimethyl Methylphosphonate 25g 500g O0208 Dimethyl (2-Oxopropyl)phosphonate 5g 25g D3875 Diphenyl 4-Bromo-α-chlorobenzylphosphonate 5g 25g D3824 Diphenyl α-Chlorobenzylphosphonate 1g 5g D3709 Diphenyl (N-Methoxy-N-methylcarbamoylmethyl)phosphonate 1g 5g D2547 Ethyl Diphenylphosphonoacetate 1g 5g D2548 Ethyl Di-o-tolylphosphonoacetate 1g M1210 Methoxymethyl(diphenyl)phosphine Oxide 5g 25g D2873 Methyl Diethylphosphonoacetate 5g 25g T1582 Tetraethyl p-Xylylenediphosphonate 5g 25g 100g M1319 Tetraisopropyl Methylenediphosphonate 25g F0340 Triethyl 2-Fluoro-2-phosphonoacetate 1g 5g D1523 Triethyl Phosphonoacetate 25g 100g 500g T2135 Triethyl 2-Phosphonopropionate 25g D1524 Triethyl 3-Phosphonopropionate 25g 250g P1265 Trimethyl Phosphonoacetate 25g 250g
Organotitanium Reagents
Product No. Product Name Unit Size D4100 Dimethyltitanocene (5% in Tetrahydrofuran/Toluene) 100g C1411 Tebbe Reagent (ca. 0.5mol/L in Toluene) 25mL T2052 Titanium(IV) Chloride (14% in Dichloromethane, ca. 1.0mo

reagent guide synthetic organic chemistry & materials chemistry

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